Naphthindazole-4,9-quinones

ABSTRACT

Naphthindazole-4,9-quinones of the formula ##STR1## where R 1  to R 5  have the meanings given in the disclosure, and their use for combating unwanted plant growth.

This is a divisional of application Ser. No. 567,627, filed Aug. 15,1990, now U.S. Pat. No. 5,117,005 which is a divisional of applicationSer. No. 407,318, filed Sep. 14, 1989 now U.S. Pat. No. 5,007,954.

The present invention relates to naphthindazole-4,9-quinones and usethereof for controlling undesirable plant growth.

It has already been disclosed that indazolequinone derivatives haveherbicidal properties (DE-A-2,107,053). Furthermore,naphthindazole-4,9-quinones are known from Chem. Ber. 97 (1964), 2555,and from Liebigs Ann. Chem. (1985), 251, but nothing is said about theiruse.

We have found that naphthindazole-4,9-quinones of the formula ##STR2##where R¹ is hydrogen, C₁ -C₁₀ -alkyl, C₂ -C₁₀ -alkenyl, C₂ -C₁₀-alkynyl, C₁ -C₁₀ -haloalkyl, C₁ -C₁₀ -hydroxyalkyl, C₂ -C₁₄-alkoxyalkyl, C₂ -C₁₄ -alkylthioalkyl, C₃ -C₇ -cycloalkyl, C₁ -C₄-alkylcarbonyloxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyloxy-C₁ -C₄-alkyl, unsubstituted or halogen-, C₁ -C₄ -alkyl- or C₁ -C₄-alkoxy-substituted (in the phenyl) phenylaminocarbonyloxy-C₁ -C₄-alkyl, unsubstituted or halogen-, C₁ --C₄ -alkyl- or C₁ -C₄-alkoxy-substituted (in the phenyl) phenylsulfonyloxy-C₁ -C₄ -alkyl, C₁-C₄ -alkoxycarbonyl-C₁ -C₄ -alkyl, hydroxycarbonyl-C₁ -C₄ -alkyl,aminocarbonyl-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyl-C₁ -C₄ -alkyl,di(C_(1-C) ₄ -alkyl)aminocarbonyl-C₁ -C₄ -alkyl, halogen-C₃ -C₄-alkynyl, unsubstituted or halogen- or C₁ -C₄ -alkyl-substitutedheteroaryl of one or two nitrogen atoms, unsubstituted or halogen-,hydroxyl-, nitro-, amino-, C.sub. 1 -C₄ -alkylamino-, di-C₁ -C₄-alkylamino-, cyano-, C₁ -C₄ -alkyl-, C₁ -C₄ -alkoxy-, C₁ -C₄-haloalkoxy-, C₁ -C₄ -haloalkyl-, C₁ -C₄ -alkylthio- or C₁ --C₄-haloalkylthio-substituted phenyl or unsubstituted orhalogen-substituted benzyl and

R², R³, R⁴ and R⁵ are each independently of the other hydrogen, halogen,nitro, cyano, hydroxyl, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄-alkylamino, C₁ -C₆ -alkyl, C₁ -C₅ -haloalkyl, C₁ -C₅ -alkoxy, C₁ -C₅-haloalkoxy, C₁ -C₅ -alkylthio, C₁ -C₅ -haloalkylthio,

C₂ -C₁₀ -alkoxyalkyl, carboxyl, C₂ -C₆ -alkoxycarbonyl, C₂ -C₆-alkanoyloxy, C₂ -C₆ -haloalkanoyloxy, C₁ -C₄ -alkylcarbonylaminc, C₁-C₄ -alkylaminocarbonyl, di(C₁ -C₄ -alkyl)aminocarbonyl, orunsubstituted or halogen-, trifluoromethyl-, nitro-, cyano-, amino-, C₁-C₄ -alkoxy-, C₁ -C₄ -alkylthio- or C₁ -C₅ -haloalkylthio-substituted

phenyl or heteroaryl

and in addition

R³ and R⁴ together with the two carbon atoms of the phenyl ring to whichthey are bonded form a heterocyclic ring or an unsubstituted orhalogen-, nitro-, cyano-, amino-, hydroxyl-, trifluoromethyl-, C₁ -C₅-alkyl-, C₁ -C₅ -alkoxy-, C₁ -C₅ -haloalkylthio-, C₁ -C₅ -haloalkoxy- orC₁ -C₅ -alkylthio-substituted benzene or naphthalene ring, have goodherbicidal properties and are selectively active with respect to cropplants.

In the formula Ia, the radicals R¹, R², R³, R⁴ and R⁵ have the followingmeanings:

R¹ : hydrogen, C₁ -C₁₀ -alkyl, preferably C₁ -C₄ -alkyl, C₂ -C₁₀-alkenyl, preferably C₂ -C₄ -alkenyl, C₂ -C₁₀ -alkynyl, preferably C₂-C₄ -alkynyl, C₁ -C₁₀ -hydroxyalkyl, preferably C₁ -C₄ -hydroxyalkyl, C₂-C₁₄ -alkoxyalkyl, preferably C₂ -C₆ -alkoxyalkyl, C₂ -C₁₄-alkylthioalkyl, preferably C₂ -C₆ -alkylthioalkyl, C₃ -C₇ -cycloalkyl,preferably C₃ -C₆ -cycloalkyl, C₁ -C₄ -alkylcarbonyloxy-C₁ -C₄ -alkyl,C₁ -C₄ -alkylaminocarbonyloxy-C₁ -C₄ -alkyl, unsubstituted or halogen-,C₁ -C₄ -alkyl- or C₁ -C₄ -alkoxy-substituted (in the phenyl)phenylaminocarbonyloxy-C₁ -C₄ -alkyl, unsubstituted or halogen-, C₁ -C₄-alkyl- or C₁ -C₄ -alkoxy-substituted (in the phenyl)phenylsulfonyloxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonyl-C₁ -C₄ -alkyl,hydroxycarbonyl-C₁ -C₄ -alkyl, aminocarbonyl-C₁ -C₄ -alkyl, C₁ -C₄-alkylaminocarbonyl-C₁ -C₄ -alkyl, di(C₁ -C₄ -alkyl)aminocarbonyl-C₁ -C₄-alkyl, halo-C₃ -C₄ -alkynyl, unsubstituted or halogen- or C₁ -C₄-alkyl-substituted heteroaryl of one or two nitrogen atoms, eg.pyrimidyl, pyridyl or imidazolyl, unsubstituted or halogen-, hydroxyl-,nitro-, amino-, C₁ -C₄ -alkylamino-, di-C₁ -C₄ -alkylamino-, cyano-, C₁-C₄ -alkyl-, C₁ -C₄ -haloalkyl-, C₁ -C₄ -alkoxy-, C₁ -C₄ -haloalkoxy-,C₁ -C₄ -alkylthio- or C₁ -C₄ -haloalkylthio-monosubstituted orpolysubstituted phenyl, unsubstituted or halogen-monosubstituted or-poly-substituted (in the phenyl) benzyl, for example methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl,n-pentyl, tert.-amyl, n-hexyl, pentyl-3, 1,2-dimethyl-n-propyl,1,3-dimethyl-n-butyl, 1-ethyl-2-methyl-n-propyl,1,2,2-trimethyl-n-propyl, 1,2-dimethyl-4-hexyl, allyl, methallyl,crotyl, 2-ethylhex-2-enyl, hex-5-enyl, 2-methylbut-2-enyl,2-methylbut-3-enyl, but-1-en-3-yl, 2-methylbut-1-en-4-yl,2-methylbut-2-en-4-yl, 3-methylbut-1-en-3-yl, propargyl, but-1-yn-3-yl,but-2-ynyl, 2-chloroethyl, 2-chloro-n-propyl, 3-chloro-n-propyl,2-chloro-sec.-butyl, 2-chloroisobutyl, 2-fluoro-sec.-butyl,2-fluoroisobutyl, 2-fluoroisopropyl, chloro-tert.-butyl,2,2,2-trifluoroethyl, hydroxymethyl, 2-hydroxyethyl, 3-hydroxy-n-propyl,2-hydroxyisopropyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl,4-hydroxy-n-butyl, 2-hydroxyisobutyl, 2-methoxyethyl, 2-ethoxyethyl,3-methoxy-n-propyl, 2-methoxyisopropyl, 3-methoxy-n-butyl,1-methoxy-sec.-butyl, methoxy-tert.-butyl, ethoxy-tert. -butyl,2-methoxy-n-butyl, 4-methoxy-n-butyl, cyclopropyl, cyclopentyl,cyclohexyl, 2-methylmercaptoethyl, 2-ethylmercaptoethyl,3-methylmercapto-n-propyl, 3-methylmercapto-n-butyl,1-methylmercapto-sec.-butyl, methylmercapto-tert.-butyl,2-methylmercapto-n-butyl, phenyl, 4-chlorophenyl, 3,4-dichlorophenyl,o-, m- or p-tert-butylphenyl, o- , m- or p-methoxyphenyl, o-, m- orp-methylphenyl, 4-methoxy-3-chlorophenyl, 2-methyl-4-chlorophenyl,benzyl, 2,6-dichlorobenzyl, 2-chloro-6-fluorobenzyl, 2,6-difluorobenzylor o-, m- or p-chlorobenzyl.

R², R³, R⁴, R⁵ : hydrogen, halogen, such as fluorine, chlorine, bromineor iodine, nitro, cyano, hydroxyl, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄-alkylamino, C₁ -C₆ -alkyl, preferably C₁ -C₄ -alkyl, C₁ -C₅ -haloalkyl,preferably C₁ -C₃ -haloalkyl, C₁ -C₅ -alkoxy, preferably C₁ -C₃ -alkoxy,C₁ -C₅ -haloalkoxy, preferably C₁ --C₃ -haloalkoxy, C₁ -C₅ -alkylthio,preferably C₁ -C₃ -alkylthio, C₁ -C₅ -haloalkylthio, preferably C₁ -C₃-haloalkylthio, C₂ -C₁₀ -alkoxyalkyl, preferably C₂ -C₆ -alkoxyalkyl,carboxyl, C₂ -C₆ -alkoxycarbonyl, preferably C₂ -C₄ -alkoxycarbonyl, C₂-C₆ -alkanoyloxy, preferably C₂ -C₄ -alkanoyloxy, C₃ -C₅-haloalkanoyloxy, preferably C₂ -C₄ -haloalkanoyloxy, C₁ -C₄-alkylcarbonylamino, C₁ -C₄ -alkylaminocarbonyl, di(C₁ -C₄-alkyl)-aminocarbonyl, unsubstituted or halogen-, preferably chlorine-or fluorine-, trifluoromethyl-, nitro-, cyano-, amino-, C₁ -C₄ -alkoxy-,C₁ -C₄ -alkylthio- or C₁ -C₅ -haloalkylthio-substituted phenyl orheteroaryl, preferably pyridyl, pyrimidyl, thienyl, furyl orbenzimidazolyl, eg. methylamino, dimethylamino, ethylamino,diethylamino, isopropylamino, diisopropylamino, methylethylamino, n-,iso- or tert.-butylamino, methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec.-butyl, tert.-butyl, n-pentyl, tert.-amyl, n-hexyl,pentyl-3, 1,2-dimethyl-n-propyl, 1,3-dimethyl-n-butyl,1-ethyl-2-methyl-n-propyl, 1,2,2-trimethyl-n-propyl,1,2-dimethyl-n-hexyl, allyl, methallyl, crotyl, 2-ethylhex-2-enyl,hex-5-enyl, 2-methylbut-2-enyl, 2-methylbut-3-enyl, but-1-en-3-yl,2-methylbut-1-en-4-yl, 2-methylbut-2-en-4-yl, 3-methylbut-1-en-3-yl,propargyl, but-1-yn-3-yl, but-2-ynyl, fluoromethyl, chloromethyl,trifluoromethyl, difluoromethyl, trichloromethyl, dichloromethyl,2-chloroethyl, 2-chloro-n-propyl, 3-chloro-n-propyl, 2-chloroisopropyl,pentafluoroethyl, 2,2,2-trifluoroethyl, 2-fluoroisopropyl,3-fluoro-n-propyl, 2-fluoroethyl, methoxy, ethoxy, n- or isopropoxy, n-,iso- or tert.-butoxy, pentoxy, difluoromethoxy, trifluoromethoxy,trichloromethoxy, methylthio, ethylthio, n- or isopropylthio, n-, iso-or tert.-butylthio, difluoromethylthio, trifluoromethylthio,methoxymethyl, ethoxymethyl, 2-methoxyethyl, 3-methoxy-n-propyl,2-methoxyisopropyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 2-ethoxyisopropyl,methoxycarbonyl, ethoxycarbonyl, n- or isopropoxycarbonyl, n-, iso-ortert.-butoxycarbonyl, 2-methoxyethoxycarbonyl, ethoxymethoxycarbonyl,2-ethoxyethoxycarbonyl, phenyl, o-, m- or p-fluorophenyl, o-, m- orp-chlorophenyl, 2,4-difluorophenyl, 2,4-p-trifluoromethylphenyl, 2-,3-and 4-nitrophenyl, 2-, 3- and 4-cyanophenyl, 2-, 3-and 4-aminophenyl,2-, 3- and 4-methoxyphenyl, 2,4-dimethoxyphenyl, 2,4,5-trimethoxyphenyl,2-, 3- and 4-thiomethylphenyl, heteroaryl such as pyrid-2-yl,pyrid-3-yl, pyrid-4-yl, thien-2-yl, thien-3-yl, fur-2-yl, fur-3-yl,benzimidazol-2-yl,3-chloropyrid-6-yl,2-methylfur-5-yl,2-methylthien-5-yl and 4,6-dimethylpyrimid-2-yl, acetyl, propionyl,butyryl, isobutyryl, valeroyl, isovaleroyl, pivaloyl, chloroacetyl,dichloroacetyl, trichloroacetyl, fluoroacetyl, difluoroacetyl,trifluoroacetyl, 3,3,3-trifluoropropionyl, pentafluoropropionyl,2-chloropropionyl, 2,2-dichloropropionyl, 2-fluoropropionyl or2,2-difluoropropionyl.

R³ and R⁴ may also form together with the two carbon atoms of the phenylring to which they are bonded an unsubstituted or fluorine-, chlorine-,bromine-, nitro-, cyano-, amino-, hydroxyl-, trifluoromethyl-, C₁ -C₅-alkyl-, preferably C₁ -C₃ -alkyl-, C₁ -C₅ -alkoxy-, C₁ -C₅-haloalkylthio-, C₁ -C₅ -haloalkoxy- or C₁ -C₅ -alkylthio-, preferablyC₁ -C₃ -alkylthio-, substituted benzene or naphthalene ring.

Examples of heterocyclic rings formed by R³ and R⁴ together with the twocarbon atoms of the phenyl ring to which they are bonded are1,4-dioxane, 1,3-dioxolane, pyrazole, indole, thiophene, triazole andpiperazine. Examples of the corresponding substituted rings are2,2-dimethyl-1,3-dioxalane, 1-methylpyrazole,1-methylindole,N,N'-dimethylpiperazine, 2,2-diphenyl-1,3-dioxolane, and2-oxo-1,3-dioxolane.

Naphthindazole-4,9-quinones of the formula Ia where R¹ is C₁ -C₄ -alkylor C₂ -C₄ -alkenyl are preferred. Preference is further given to thosecompounds of the formula Ia where the substituents R² to R⁵ are eachindependently of the others hydrogen, hydroxyl, halogen, nitro, cyano,amino, C₁ -C₄ -alkylamino or di-C₁ -C₄ -alkylamino. Preference is givenin particular to compounds where R² to R⁵ are each hydrogen, hydroxyl orhalogen.

The naphthindazole-4,9-quinones of the formula ##STR3## where R¹, R²,R³, R⁴ and R⁵ are each as defined for the formula Ia, with the provisothat R¹ is not hydrogen or methyl, are novel.

The naphthindazole-4,9-quinones of the formula I are obtained byreacting the 5-arylmethylpyrazol-4-yl carbonyl halides of the formula##STR4## where R¹, R², R³, R⁴ and R⁵ are each as defined above and Halis halogen, in an inert solubilizer in the presence of a Friedel-Craftscatalyst, and converting the resulting compounds of the formula ##STR5##where R¹, R², R³, R⁴ and R⁵ are each as defined above, in the presenceof a diluent with oxidizing agents into the naphthindazole-4,9-quinonesof the formula I.

Suitable inert solubilizers for this purpose are carbon disulfide,nitromethane, nitrobenzene, 1,2-dichloroethane,1,1,2,2-tetrachloroethane, sulfolane, trichloroethylene and1,1,1-trichloroethane.

Suitable Friedel-Crafts catalysts are aluminum trichloride, borontrifluoride, tin tetrachloride, titanium tetrachloride, zinc chloride,boron trichloride, trifluoroacetic acid, sulfuric acid, aluminumbromide, gallium chloride, iron(III) chloride, antimony pentachloride,antimony trichloride and zirconium tetrachloride. The amount of catalystis from 5 to 500, preferably from 100 to 250, mol %, based on startingacid chloride of the formula II.

The reaction advantageously takes place at from 0° to 150° C.

The oxidation of compounds III is advantageously carried out in an inertdiluent, such as acetic acid or alcoholic alkali metal hydroxidesolution, in the presence or absence of water, at from 0° to 120° C.Suitable oxidizing agents are hydrogen peroxide and chromium(IV) oxide.

The oxidation is advantageously carried out by dissolving the startingcompounds III in dilute, aqueous-alcoholic solutions of alkali metalhydroxides at temperatures of from 0° C. to 120° C., preferably from 50°C. to 100° C., and adding excess aqueous hydrogen peroxide solution. Thereaction will in general have ended after 4-8, but not more than 24,hours. The solid end product is filtered off with suction and may berecrystallized or chromatographed for purification.

The synthesis of the 5-arylmethylpyrazol-4-yl carbonyl halides II can beeffected in a conventional manner in accordance with the followingscheme: ##STR6## (Y. Oikana, K. Sugano and 0. Yonemitsu, J. Org. Chem.43 (1978), 2087) ##STR7## (G. Menozzi, L. Mosti and P. Schenone, J.Heterocycl. Chem. 24 (1987), 1969) ##STR8##

The naphthindazole-4,9-quinones of the formula I are likewise obtainedon reacting substituted 1,4-naphthoquinones of the formula ##STR9##where R², R³, R⁴ and R⁵ are each as defined above, with diazomethane inthe presence of inert diluents, for example aliphatic or alicyclicethers, oxidizing the resulting compounds of the formula ##STR10## whereR², R³, R⁴ and R⁵ are each as defined above, in an inert diluent andalkylating the resulting naphthindazole-4,9-quinones of the formula##STR11## where R², R³, R⁴ and R⁵ are each as defined above, with analkylating agent of the formula

    R.sup.1 --X                                                (VII)

where

R¹ is as defined above and

X is p-toluenesulfonate, mesylate, brosylate, halogen or a group of theformula ##STR12## where R¹ is as defined above, in a diluent in thepresence of a base at from -30° C. to +100° C.

The reaction of the 1,4-naphthoquinones IV with diazomethane can becarried out in a conventional manner (Houben-Weyl, Methoden der org.Chemie, volume 7/3a, page 553 (1977)). The oxidation of compounds V ispossible inter alia with hydrogen peroxide, chromium(VI) oxide oratmospheric oxygen in an inert diluent, such as dilute acetic acid ormethyl t-butyl ether.

The alkylation of the naphthindazole-4,9-quinones VI with the alkylatingagent VII takes place in a conventional manner in a diluent, for examplewater or acetone or mixtures thereof, in the presence of a base, such asalkali metal or alkaline earth metal hydroxides, alkali metal oralkaline earth metal carbonates or alkali metal or alkaline earth metalbicarbonates. It is preferable to work at from 10° to 30° C.

All the other starting compounds and reaction products whose preparationhas not been described in detail are either known or can be prepared byknown principles.

Preparation Examples EXAMPLE 1 ##STR13##

A suspension of 20.6 g (0.13 mol) of 1,4-naphthoquinone in 500 ml ofmethylt-butyl ether is admixed under a protective gas atmosphere at 0°C. with 400 ml of a 3.5×10⁻⁴ M solution (0.14 mol) of diazomethaneindiethyl ether. After the addition has ended, the suspension is heatedtoroom temperature, and air is passed through the reaction mixtureovernight.The precipitate formed is then filtered off with suction,washed with 100 ml of methyl t-butyl ether and stirred into 75 ml of hotethanol. It is filtered off with suction, washed with 100 ml of ethanoland dried.

Yield: 12.1 g (47% of theory)

Melting point: 180° C. decomposition

EXAMPLE 2 ##STR14##

6,0 g (0.03 mol) of naphthindazole-4,9-quinone (Example 1) are suspendedin100 ml of 80% strength aqueous acetone and admixed at room temperaturein succession with 3.2 g (0.03 mol) of sodium carbonate and 7.3 g (0.06mol) of 1-bromo-2-propene. The mixture is stirred overnight and thenrefluxed for three hours. It is cooled down, admixed with a further 1.1g (0.01 mol) of sodium carbonate and 2.4 g (0.02 mol) of1-bromo-2-propene and refluxed for a further two hours. It is thenconcentrated under reduced pressure and extracted four times with 100 mlof dichloromethane each time. The combined extracts are dried oversodium sulfate and concentrated. The crystalline residue ischromatographed over silica gel (mobile phase: cyclohexane/ethylacetate) to obtain 4.6 g (64% of theory) of1-(propen-2-yl)naphthindazole-4,9-quinone of melting point 105°-108° C.

EXAMPLE 3 ##STR15##

a) 1.25 g (0.005 mol) of 5-(4-chlorophenylmethyl)-1-methylpyrazol-4-ylcarboxylic acid (preparation: G. Menozzi, L. Mosti and P. Schenone, J.Heterocycl. Chem. 24 (1987), 1669) are dissolved in 2 ml of thionylchloride and refluxed for one hour. Excess thionyl chloride is thenremoved under reduced pressure (12 mmHg), the residue is taken up in 20mlof diethyl ether, and the mixture is stirred with 2.0 g of activecharcoal.The mixture is filtered after 30 minutes, the filtrate isconcentrated under reduced pressure to give 1.25 g (93% of theory) ofacid chloride as a colorless oil.

b) 1.25 g (4.6 mmol) of 5-(4-chlorophenylmethyl)-1-methylpyrazol-4-ylcarbonyl chloride are dissolved in 5 ml of nitromethane and added to a0° C. solution of 1.85 g (14 mmol) of aluminum chloride in 20 mlofnitromethane. The mixture is stirred at room temperature overnight andthenpoured into a mixture of 50 g of ice and 20 ml of concentratedhydrochloricacid. The organic phase is separated off, the aqueous phaseis extracted twice more with 50 ml of dichloromethane each time and thecombined extracts are dried over sodium sulfate. Removing the solventunder reducedpressure leaves 1.10 g (100% of theory) of6-chloro-9-hydro-1-methylnaphthindazol-4-one of melting point >270°C.

¹ H-NMR (250 MHz, DMSO-d₆): 4.05 (s; 3H), 4.45 (s; 2H), 7.35 (dd,J=9.2and 0.2 Hz; 1H), 7.90 (d,J=9.0 Hz; 1H), 8.20 (d, J=0.2 Hz; 1H), 8.45 (s;1H)

c) 1.10 g (4.6 mmol) of 6-chloro-9-hydro-1-methylnaphthindazol-4-one aredissolved in a mixture of 10 ml of 10% strength sodium hydroxidesolution and 50 ml of methanol by heating (80° C.). The solution iscooled down to 60° C., and 5 ml of a 30% strength solution of hydrogenperoxide are added. The mixture is stirred at room temperatureovernight, and the precipitated quinone is then filtered off withsuction, giving 0.85 g (57% of theory) of1-methyl-6-chloronaphthindazol-4,9-quinone of melting point 219° C.

¹ H-NMR (250 MHz, CDCl₃): 4.35 (s; 3H), 7.72 (d, J=9.0 Hz; 1H), 8.05 (s;1H), 8.18 (s; 1H), 8.18 (d, J=9.0 Hz; 1H).

The following compounds of the formulae I and Ia can be obtained in asimilar manner:

    __________________________________________________________________________    Example no.                                                                            R.sup.1               R.sup.2 -R.sup.5                                                                      Melting poimt [°C.]             __________________________________________________________________________    4        CH.sub.3              H       181                                    5        CH.sub.2 CH.sub.3     H       151-152                                6        isopropyl             H       126                                    7        n-propyl              H                                              8        n-butyl               H        69                                    9        t-butyl               H       152                                    10       2-pentyl              H       164                                    11       cyclopentyl           H                                              12       cyclohexyl            H       148                                    13       CH.sub.2CF.sub.3      H       171                                    14       CH.sub.2OH            H                                              15       CH.sub.2CH.sub.2OH    H       158                                    16                                                                                      ##STR16##            H       109                                    17                                                                                      ##STR17##            H       116                                    18                                                                                      ##STR18##            H       179                                    19                                                                                      ##STR19##            H       155                                    20       CH.sub.2COOC.sub.2 H.sub. 5                                                                         H       149                                    21       CH.sub.2COOH          H                                              22                                                                                      ##STR20##            H                                              23                                                                                      ##STR21##            H                                              24                                                                                      ##STR22##            H                                              25       CH.sub.2 CH.sub.2SCH.sub.3                                                                          H                                              26       CH.sub.2SCH.sub.3     H                                              27       CH.sub.2CCH           H       193                                    28       CH.sub.2CCBr          H                                              29       phenyl                H       221                                    30       benzyl                H       154                                    31       2-(4,6-dimethylpyrimidinyl)                                                                         H       237                                    32       2-pyridinyl           H       221                                    33       2-(2-imidazoline)     H                                              34       2,4-dichlorophenyl    H                                              35       2,4,6-trichlorophenyl H                                              36       4-fluorophenyl        H                                              37       2,4-difluorophenyl    H                                              38       2,4,6-trifluorophenyl H                                              39       4-methoxyphenyl       H                                              40       2,4-dimethoxyphenyl   H                                              41       4-thiomethylphenyl    H                                              42       4-trifluoromethylphenyl                                                                             H                                              __________________________________________________________________________    Example no.                                                                          R.sup.1 R.sup.2 R.sup.3                                                                            R.sup.4                                                                            R.sup.5                                                                              Melting point [°C.]            __________________________________________________________________________    43     CH.sub.3                                                                              F       H    H    H      195                                   44     CH.sub.3                                                                              H       F    H    H                                            45     CH.sub.3                                                                              H       H    F    H      173                                   46     CH.sub.3                                                                              H       H    H    F                                            47     CH.sub.3                                                                              Cl      H    H    H                                            48     CH.sub.3                                                                              H       Cl   H    H      219                                   49     CH.sub.3                                                                              H       H    Cl   H      226                                   50     CH.sub.3                                                                              H       H    H    Cl                                           51     CH.sub.3                                                                              Br      H    H    H                                            52     CH.sub.3                                                                              H       H    H    Br     190-192                               53     CH.sub.3                                                                              Cl      H    H    Cl                                           54     CH.sub.3                                                                              H       Cl   H    Cl     230                                   55     CH.sub.3                                                                              H       Cl   Cl   H                                            56     CH.sub.3                                                                              F       H    H    F                                            57     CH.sub.3                                                                              H       F    H    F                                            58     CH.sub.3                                                                              H       F    F    H                                            59     CH.sub.3                                                                              OH      H    H    H      190                                   60     CH.sub.3                                                                              H       OH   H    H                                            61     CH.sub.3                                                                              H       H    OH   H                                            62     CH.sub.3                                                                              H       H    H    OH     212                                   63     CH.sub.3                                                                              OH      H    H    OH     224-227                               64     CH.sub.3                                                                              OCH.sub.3                                                                             H    H    H                                            65     CH.sub.3                                                                              H       OCH.sub.3                                                                          H    H      193                                   66     CH.sub.3                                                                              H       H    OCH.sub.3                                                                          H      173                                   67     CH.sub.3                                                                              H       H    H    OCH.sub.3                                                                            230                                   68     CH.sub.3                                                                              OCH.sub.3                                                                             H    CH.sub.3                                                                           H      212-213                               69     CH.sub.3                                                                              OH      H    H    OCH.sub.3                                    70     CH.sub.3                                                                              OCH.sub.3                                                                             H    H    OH                                           71     CH.sub.3                                                                              OCH.sub.3                                                                             OCH.sub.3                                                                          H    OCH.sub.3                                    72     CH.sub.3                                                                              OH      OCH.sub.3                                                                          H    OCH.sub.3                                    73     CH.sub.3                                                                              OCH.sub.3                                                                             H    OCH.sub.3                                                                          H      212                                   74     CH.sub.3                                                                              OCH.sub.3                                                                             H    OCH.sub.3                                                                          OH                                           75     CH.sub.3                                                                              OH      H    OCH.sub.3                                                                          H      208                                   76     CH.sub.3                                                                              H       OCH.sub.3                                                                          H    OCH.sub.3                                    77     CH.sub.3                                                                              H       OCH.sub.3                                                                          H    OH                                           78     CH.sub.3                                                                              H       OCH.sub.2CH.sub.2 O                                                                     H                                            79     CH.sub.3                                                                              H       OCH.sub.2O                                                                              H      252                                   80     CH.sub.3                                                                              H       OH   OH   H                                            81     CH.sub.3                                                                              SCH.sub.3                                                                             H    H    H                                            82     CH.sub.3                                                                              H       SCH.sub.3                                                                          H    H                                            83     CH.sub.3                                                                              H       H    SCH.sub.3                                                                          H                                            84     CH.sub.3                                                                              H       H    H    SCH.sub.3                                    85     CH.sub.3                                                                               ##STR23##                                                                            H    H    H      220                                   86     CH.sub.3                                                                              H       H    H                                                                                   ##STR24##                                   87     CH.sub.3                                                                              CH.sub.3                                                                              H    H    H                                            88     CH.sub.3                                                                              H       CH.sub.3                                                                           H    H      177                                   89     CH.sub.3                                                                              H       H    CH.sub.3                                                                           H      136                                   90     CH.sub.3                                                                              H       H    H    CH.sub.3                                                                             218                                   91     CH.sub.3                                                                              CH.sub.3                                                                              H    H    CH.sub.3                                                                             143                                   92     CH.sub.3                                                                              CF.sub.3                                                                              H    H    H                                            93     CH.sub.3                                                                              H       CF.sub.3                                                                           H    H                                            94     CH.sub.3                                                                              H       H    CF.sub.3                                                                           H                                            95     CH.sub.3                                                                              H       H    H    CF.sub.3                                     96     CH.sub.3                                                                              H       CH.sub.3                                                                           H    OH     154                                   97     CH.sub.3                                                                              OH      H    CH.sub.3                                                                           H      175                                   98     CH.sub.3                                                                              H       C.sub.4 H.sub.4                                                                         OH     288                                   99     CH.sub.3                                                                              H       C.sub. 4 H.sub.4                                                                        H                                            100    CH.sub.3                                                                              OH      C.sub.4 H.sub.4                                                                         H                                            101    CH.sub.3                                                                              H       C.sub.4 H.sub.4                                                                          ##STR25##                                                                           253                                   102    CH.sub.3                                                                               ##STR26##                                                                            C.sub.4 H.sub.4                                                                         H      231                                   103    CH.sub.3                                                                              F       C.sub.4 H.sub.4                                                                         OH                                           104    CH.sub.3                                                                              NO.sub.2                                                                              H    H    H                                            105    CH.sub.3                                                                              H       H    H    NO.sub.2                                     106    CH.sub.3                                                                              NH.sub.2                                                                              H    H    H                                            107    CH.sub.3                                                                              H       H    H    NH.sub.2                                     108    CH.sub.3                                                                               ##STR27##                                                                            H    H    H                                            109    CH.sub.3                                                                              H       H    H                                                                                   ##STR28##                                   110    CH.sub.3                                                                              CN      H    H    H                                            111    CH.sub.3                                                                              H       CN   H                                                 112    CH.sub.3                                                                              H       H    H    CN                                           113    CH.sub.3                                                                              C.sub.6 H.sub.5                                                                       H    H    H                                            114    CH.sub.3                                                                              H       C.sub.6 H.sub.5                                                                    H    H      185                                   115    CH.sub.3                                                                              H       H    C.sub.6 H.sub.5                                                                    H                                            116    CH.sub.3                                                                              H       H    H    C.sub.6 H.sub.5                              117    CH.sub.3                                                                              COOCH.sub.3                                                                           H    H    H                                            118    CH.sub.3                                                                              H       H    H    COOCH.sub.3                                  119    CH.sub.3                                                                              COOH    H    H    H                                            120    CH.sub.3                                                                              H       H    H    COOH                                         121    CH.sub.3                                                                              CONHCH.sub.3                                                                          H    H    H                                            122    CH.sub.3                                                                              H       H    H    CONHCH.sub.3                                 123    CH.sub.3                                                                              CON(CH.sub.3).sub.2                                                                   H    H    H                                            124    CH.sub.3                                                                              H       H    H    CON(CH.sub.3).sub.2                          125    C.sub.6 H.sub.5                                                                       OH      H    H    OH     208                                   126    C.sub.6 H.sub.5                                                                       OH      H    H    H                                            127    C.sub.6 H.sub.5                                                                       H       H    H    OH                                           128    C.sub.6 H.sub.5                                                                       F       H    H    H                                            129    C.sub.6 H.sub.5                                                                       H       H    F    H                                            130    C.sub.6 H.sub.5                                                                       H       H    H    F                                            131    C.sub.6 H.sub.5                                                                       Cl      H    H    H                                            132    C.sub.6 H.sub.5                                                                       H       H    H    Cl                                           133    C.sub.6 H.sub.5                                                                       OH      H    OCH.sub.3                                                                          H                                            134    C.sub.6 H.sub.5                                                                       OCH.sub.3                                                                             H    OH   H                                            135    C.sub.6 H.sub.5                                                                       H       OCH.sub.3                                                                          H    OH                                           136    C.sub.6 H.sub.5                                                                       CF.sub.3                                                                              H    H    H                                            137    C.sub.6 H.sub.5                                                                       H       H    CF.sub.3                                                                           H                                            138    C.sub.6 H.sub.5                                                                       H       H    H    CF.sub.3                                     139    C.sub.6 H.sub.5                                                                       NH.sub.2                                                                              H    H    H                                            140    C.sub.6 H.sub.5                                                                       H       H    NH.sub.2                                                                           H                                            141    C.sub.6 H.sub.5                                                                       H       H    H    NH.sub.2                                     142    C.sub.6 H.sub.5                                                                       H       NO.sub.2                                                                           H    H                                            143    C.sub.6 H.sub.5                                                                       NO.sub.2                                                                              H    H    H                                            144    C.sub.6 H.sub.5                                                                       F       F    H    H                                            145    isopropyl                                                                             H       CF.sub.3                                                                           H    H                                            146    isopropyl                                                                             H       H    CF.sub.3                                                                           H                                            147    isopropyl                                                                             H       H    H    CF.sub.3                                     148    isopropyl                                                                             H       CH.sub.3                                                                           H    OH                                           149    isopropyl                                                                             OH      H    CH.sub.3                                                                           H                                            150    isopropyl                                                                             H       C.sub.4 H.sub.4                                                                         OH                                           151    isopropyl                                                                             H       C.sub.4 H.sub.4                                                                         H                                            152    isopropyl                                                                             OH      C.sub.4 H.sub.4                                                                         H                                            153    isopropyl                                                                             H       C.sub.4 H.sub.4                                                                          ##STR29##                                   154    isopropyl                                                                              ##STR30##                                                                            C.sub.4 H.sub.4                                                                         H                                            155    isopropyl                                                                             F       C.sub.4 H.sub.4                                                                         OH                                           156    isopropyl                                                                             NO.sub.2                                                                              H    H    H                                            157    isopropyl                                                                             H       H    H    NO.sub.2                                     158    isopropyl                                                                             NH.sub.2                                                                              H    H    H                                            159    isopropyl                                                                             H       H    H    NH.sub.2                                     160    isopropyl                                                                              ##STR31##                                                                            H    H    H                                            161    isopropyl                                                                             H       H    H    NHCOCH.sub.3                                 162    isopropyl                                                                             CN      H    H    H                                            163    isopropyl                                                                             H       CN   H    H                                            164    isopropyl                                                                             H       H    H    CN                                           165    isopropyl                                                                             C.sub.6 H.sub.5                                                                       H    H    H                                            166    isopropyl                                                                             H       C.sub.6 H.sub.5                                                                    H    H                                            167    isopropyl                                                                             H       H    C.sub.6 H.sub.5                                                                    H                                            168    isopropyl                                                                             H       H    H    C.sub.6 H.sub.5                              169    isopropyl                                                                             COOCH.sub.3                                                                           H    H    H                                            170    isopropyl                                                                             H       H    H    COOCH.sub.3                                  171    isopropyl                                                                             F       H    H    H                                            172    isopropyl                                                                             H       F    H    H                                            173    isopropyl                                                                             H       H    F    H                                            174    isopropyl                                                                             H       H    H    F                                            175    isopropyl                                                                             Cl      H    H    H                                            176    isopropyl                                                                             H       Cl   H    H                                            177    isopropyl                                                                             H       H    Cl   H                                            178    isopropyl                                                                             H       H    H    Cl                                           179    isopropyl                                                                             Br      H    H    H                                            180    isopropyl                                                                             F       H    H    Br                                           181    isopropyl                                                                             Cl      H    H    Cl                                           182    isopropyl                                                                             H       Cl   H    Cl                                           183    isopropyl                                                                             H       Cl   Cl   H                                            184    isopropyl                                                                             F       H    H    F                                            185    isopropyl                                                                             H       F    H    F                                            186    isopropyl                                                                             H       F    F    H                                            187    isopropyl                                                                             OH      H    H    H                                            188    isopropyl                                                                             H       OH   H    H                                            189    isopropyl                                                                             H       H    OH   H                                            190    isopropyl                                                                             H       H    H    OH                                           191    isopropyl                                                                             OH      H    H    OH                                           192    isopropyl                                                                             OCH.sub.3                                                                             H    H    H                                            193    isopropyl                                                                             H       OCH.sub.3                                                                          H    H      176                                   194    isopropyl                                                                             H       H    OCH.sub.3                                                                          H      160                                   195    isopropyl                                                                             H       H    H    OCH.sub.3                                    196    isopropyl                                                                             OCH.sub.3                                                                             H    H    OCH.sub.3                                    197    isopropyl                                                                             OH      H    H    OCH.sub.3                                    198    isopropyl                                                                             OCH.sub.3                                                                             H    H    OH                                           199    isopropyl                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                          H    OCH.sub.3                                    200    isopropyl                                                                             OH      OCH.sub.3                                                                          H    OCH.sub.3                                    201    isopropyl                                                                             OCH.sub.3                                                                             H    OCH.sub.3                                                                          OCH.sub.3                                    202    isopropyl                                                                             OCH.sub.3                                                                             H    OCH.sub.3                                                                          OH                                           203    isopropyl                                                                             OH      H    OCH.sub.3                                                                          H                                            204    isopropyl                                                                             H       OCH.sub.3                                                                          H    OCH.sub.3                                    205    isopropyl                                                                             H       OCH.sub.3                                                                          H    OH                                           206    isopropyl                                                                             H       OCH.sub.2CH.sub.2 O                                                                     H                                            207    isopropyl                                                                             H       OCH.sub.2O                                                                              H                                            208    isopropyl                                                                             H       OH   OH   H                                            209    isopropyl                                                                             SCH.sub.3                                                                             H    H    H                                            210    isopropyl                                                                             H       SCH.sub.3                                                                          H    H                                            211    isopropyl                                                                             H       H    SCH.sub.3                                                                          H                                            212    isopropyl                                                                             H       H    H    SCH.sub.3                                    213    isopropyl                                                                              ##STR32##                                                                            H    H    H                                            214    isopropyl                                                                             H       H    H                                                                                   ##STR33##                                   215    isopropyl                                                                             CH.sub.3                                                                              H    H    H                                            216    isopropyl                                                                             H       CH.sub.3                                                                           H    H                                            217    isopropyl                                                                             H       H    CH.sub.3                                                                           H                                            218    isopropyl                                                                             H       H    H    CH.sub.3                                     219    isopropyl                                                                             CH.sub.3                                                                              H    H    CH.sub.3                                     220    isopropyl                                                                             CF.sub.3                                                                              H    H    H                                            221    isopropyl                                                                             COOH    H    H    H                                            222    isopropyl                                                                             H       H    H    COOH                                         223    isopropyl                                                                             CONHCH.sub.3                                                                          H    H    H                                            224    isopropyl                                                                             H       H    H    CONHCH.sub.3                                 225    isopropyl                                                                             CON(CH.sub.3).sub.2                                                                   H    H    H                                            226    isopropyl                                                                             H       H    H    CON(CH.sub.3).sub.2                          227    CH.sub.2CCH                                                                           OH      H    H    H                                            228    CH.sub.2CCH                                                                           H       H    H    OH                                           229    CH.sub.2CCH                                                                           OCH.sub.3                                                                             H    H    H                                            230    CH.sub.2CCH                                                                           H       H    H    OCH.sub.3                                    231    CH.sub.2CCH                                                                           OH      H    OCH.sub.3                                                                          H                                            232    CH.sub.2CCH                                                                           H       OCH.sub.3                                                                          H    OH                                           233    CH.sub.2CCH                                                                           F       H    H    H                                            234    CH.sub.2CCH                                                                           H       H    F    H                                            235    CH.sub.2CCH                                                                           H       H    H    F                                            236    CH.sub.2CCH                                                                           Cl      H    H    H                                            237    CH.sub.2CCH                                                                           H       H    H    Cl                                           238    CH.sub.2CCH                                                                           H       H    H    Br                                           239    CH.sub.2CCH                                                                           CF.sub.3                                                                              H    H    H                                            240    CH.sub.2CCH                                                                           H       H    CF.sub.3                                                                           H                                            241    CH.sub.2CCH                                                                           H       H    H    CF.sub.3                                     242    CH.sub.2CCH                                                                           H       OCH.sub.3                                                                          H    H                                            243    CH.sub.2C CH                                                                          H       H    OCH.sub.3                                                                          H                                            244    CH.sub.2CCH                                                                           CN      H    H    H                                            245    CH.sub.2CCH                                                                           H       H    CN   H                                            246    CH.sub.2CCH                                                                           H       H    H    CN                                           247    allyl   F       H    H    H                                            248    allyl   H       F    H    H                                            249    allyl   H       H    F    H                                            250    allyl   H       H    H    F                                            251    allyl   Cl      H    H    H                                            252    allyl   H       Cl   H    H                                            253    allyl   H       H    Cl   H                                            254    allyl   H       H    H    Cl                                           255    allyl   Br      H    H    H                                            256    allyl   H       H    H    Br                                           257    allyl   Cl      H    H    Cl                                           258    allyl   H       Cl   H    Cl                                           259    allyl   H       Cl   Cl   H                                            260    allyl   F       H    H    F                                            261    allyl   H       F    H    F                                            262    allyl   H       F    F    H                                            263    allyl   OH      H    H    H                                            264    allyl   H       OH   H    H                                            265    allyl   H       H    OH   H                                            266    allyl   H       H    H    OH                                           267    allyl   OH      H    H    OH                                           268    allyl   OCH.sub.3                                                                             H    H    H                                            269    allyl   H       OCH.sub.3                                                                          H    H                                            270    allyl   H       H    OCH.sub.3                                                                          H                                            271    allyl   H       H    H    H                                            272    allyl   OCH.sub.3                                                                             H    H    OCH.sub.3                                    273    allyl   OH      H    H    OCH.sub.3                                    274    allyl   OCH.sub.3                                                                             H    H    OH                                           275    allyl   OCH.sub.3                                                                             OCH.sub.3                                                                          H    OCH.sub.3                                    276    allyl   OH      OCH.sub.3                                                                          H    OCH.sub.3                                    277    allyl   OCH.sub.3                                                                             H    OCH.sub.3                                                                          OCH.sub.3                                    278    allyl   OCH.sub.3                                                                             H    OCH.sub.3                                                                          OH                                           279    allyl   OH      H    OCH.sub.3                                                                          H                                            280    allyl   H       OCH.sub.3                                                                          H    OCH.sub.3                                    281    allyl   H       OCH.sub.3                                                                          H    OH                                           282    allyl   H       OCH.sub.2CH.sub.2 O                                                                     H                                            283    allyl   H       OCH.sub.2O                                                                              H                                            284    allyl   H       OH   OH   H                                            285    allyl   SCH.sub.3                                                                             H    H    H                                            286    allyl   H       SCH.sub.3                                                                          H    H                                            287    allyl   H       H    SCH.sub.3                                                                          H                                            288    allyl   H       H    H    SCH.sub.3                                    289    allyl                                                                                  ##STR34##                                                                            H    H    H                                            290    allyl   H       H    H                                                                                   ##STR35##                                   291    allyl   CH.sub.3                                                                              H    H    H                                            292    allyl   H       CH.sub.3                                                                           H    H                                            293    allyl   H       H    CH.sub.3                                                                           H                                            294    allyl   H       H    H    H                                            295    allyl   CH.sub.3                                                                              H    H    CH.sub.3                                     296    allyl   CF.sub.3                                                                              H    H    H                                            297    allyl   H       CF.sub.3                                                                           H    H                                            298    allyl   H       H    CF.sub.3                                                                           H                                            299    allyl   H       H    H    CF.sub.3                                     300    allyl   H       CH.sub.3                                                                           H    OH                                           301    allyl   OH      H    CH.sub.3                                                                           H                                            302    allyl   H       C.sub.4 H.sub.4                                                                         OH                                           303    allyl   H       C.sub.4 H.sub.4                                                                         H                                            304    allyl   OH      C.sub.4 H.sub.4                                                                         H                                            305    allyl   H       C.sub.4 H.sub.4                                                                          ##STR36##                                   306    allyl                                                                                  ##STR37##                                                                            C.sub.4 H.sub.4                                                                         H                                            307    allyl   F       C.sub.4 H.sub.4                                                                         OH                                           308    allyl   NO.sub.2                                                                              H    H    H                                            309    allyl   H       H    H    NO.sub.2                                     310    allyl   NH.sub.2                                                                              H    H    H                                            311    allyl   H       H    H    NH.sub.2                                     312    allyl                                                                                  ##STR38##                                                                            H    H    H                                            313    allyl   H       H    H                                                                                   ##STR39##                                   314    allyl   CN      H    H    H                                            315    allyl   H       CN   H    H                                            316    allyl   H       H    H    CN                                           317    allyl   C.sub.6 H.sub.5                                                                       H    H    H                                            318    allyl   H       C.sub.6 H.sub.5                                                                    H    H                                            319    allyl   H       H    C.sub.6 H.sub.5                                                                    H                                            320    allyl   H       H    H    C.sub.6 H.sub.5                              321    allyl   COOCH.sub.3                                                                           H    H    H                                            322    allyl   H       H    H    COOCH.sub.3                                  323    allyl   COOH    H    H    H                                            324    allyl   H       H    H    COOH                                         325    allyl   CONHCH.sub.3                                                                          H    H    H                                            326    allyl   H       H    H    CONHCH.sub.3                                 327    allyl   CON(CH.sub.3).sub.2                                                                   H    H    H                                            328    allyl   H       H    H    CON(CH.sub.3).sub.2                          329    allyl   N(CH.sub.3).sub.2                                                                     H    H    H                                            330    allyl   H       H    H    N(CH.sub.3).sub.2                            331    allyl   F       H    H    NH.sub.2                                     332    allyl   NH.sub.2                                                                              H    H    F                                            __________________________________________________________________________

The active ingredients have a herbicidal action and are selective incrop plants.

The compounds, and herbicidal agents containing them, may be applied forinstance in the form of directly sprayable solutions, powders,suspensions(including high-percentage aqueous, oily or othersuspensions), dispersions, emulsions, oil dispersions, pastes, dusts,broadcasting agents, or granules by spraying, atomizing, dusting,broadcasting or watering. The forms of application depend entirely onthe purpose for which the agents are being used, but they must ensure asfine a distribution of the active ingredients according to the inventionas possible.

For the preparation of solutions, emulsions, pastes and oil dispersionsto be sprayed direct, mineral oil fractions of medium to high boilingpoint, such as Kerosene or diesel oil, further coal-tar oils, and oilsof vegetable or animal origin, aliphatic, cyclic and aromatichydrocarbons such as benzene, toluene, xylene, paraffin,tetrahydronaphthalene, alkylated naphthalenes and their derivatives suchas methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone,chlorobenzene, isophorone,etc., and strongly polar solvents such asN,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water,etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes,oil dispersions or wettable powders by adding water. To prepareemulsions,pastes and oil dispersions the ingredients as such ordissolved in an oil or solvent may be homogenized in water by means ofwetting or dispersing agents, adherents or emulsifiers. Concentrateswhich are suitable for dilution with water may be prepared from activeingredient, wetting agent,adherent, emulsifying or dispersing agent andpossibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal andammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid,phenolsulfonic acid, naphthalenesulfonic acid anddibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, alkalimetal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid,lauryl ether sulfate, fatty alcohol sulfates, and salts of sulfatedhexadecanols, heptadecanols, and octadecanols, salts of fatty alcoholglycol ethers, condensation products of sulfonated naphthalene andnaphthalene derivatives with formaldehyde, condensation products ofnaphthalene or naphthalenesulfonic acids with phenol and formaldehyde,polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol,ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenolpolyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyetheralcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylatedpolyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitolesters,lignin-sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing orgrinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules; may beprepared by bonding the active ingredients to solid carriers. Examplesof solid carriers are mineral earths such as silicic acid, silica gels,silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole,loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesiumsulfate, magnesium oxide, ground plastics, fertilizers such as ammoniumsulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetableproducts such as grain meals, bark meal, wood meal, and nutshell meal,cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90%, byweight of active ingredient.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 2 is mixed with 10 parts by weightofN-methyl-alpha-pyrrolidone. A mixture is obtained which is suitablefor application in the form of very fine drops.

II. 20 parts by weight of compound no. 4 is dissolved in a mixtureconsisting of 80 parts by weight of xylene, 10 parts by weight of theadduct of 8 to 10 moles of ethylene oxide and 1 mole of oleicacid-N-monoethanolamide, 5 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40moles of ethylene oxide and 1 mole of castor oil. By pouring thesolution into 100,000 parts by weight of water and uniformlydistributing it therein, an aqueous dispersion is obtained containing0.02% by weight of the active ingredient.

III. 20 parts by weight of compound no. 6 is dissolved in a mixtureconsisting of 40 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 7 moles of ethyleneoxide and 1 mole of isooctylphenol, and 10 parts by weight of the adductof 40 moles of ethylene oxide and 1 mole of castor oil. By pouring thesolution into 100,000 parts by weight of water and finely distributingit therein, an aqueous dispersion is obtained containing 0.02% by weightof the activeingredient.

IV. 20 parts by weight of compound no. 59 is dissolved in a mixtureconsisting of 25 parts by weight of cyclohexanone, 65 parts by weight ofamineral oil fraction having a boiling point between 210° and 280° C.,and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1mole of castor oil. By pouring the solution into 100,000 parts by weightof water and uniformly distributing it therein, anaqueous dispersion isobtained containing 0.02% by weight of the active ingredient.

V. 20 parts by weight of compound no. 45 is well mixed with 3 parts byweight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid,17parts by weight of the sodium salt of a lignin-sulfonic acid obtainedfrom a sulfite waste liquor, and 60 parts by weight of powdered silicagel, andtriturated in a hammer mill. By uniformly distributing themixture in 20,000 parts by weight of water, a spray liquor is obtainedcontaining 0.1% by weight of the active ingredient.

VI. 3 parts by weight of compound no. 4 is intimately mixed with 97parts by weight of particulate kaolin. A dust is obtained containing 3%by weight of the active ingredient.

VII. 30 parts by weight of compound no. 6 is intimately mixed with amixture consisting of 92 parts by weight of powdered silica gel and 8parts by weight of paraffin oil which has been sprayed onto the surfaceofthis silica gel. A formulation of the active ingredient is obtainedhaving good adherence.

VIII. 20 parts by weight of compound no. 59 is intimately mixed with 2parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of afatty alcohol polyglycol ether, 2 parts of the sodium salt of aphenolsulfonic acid-urea-formaldehyde condensate and 68 parts of aparaffinic mineral oil. A stable oily dispersion is obtained.

The active ingredients or the herbicidal agents containing them may beapplied pre- or postemergence. If certain crop plants tolerate theactive ingredients less well, application techniques may be used inwhich the herbicidal agents are sprayed from suitable equipment in sucha manner that the leaves of sensitive crop plants are if possible nottouched, and the agents reach the soil or the unwanted plants growingbeneath the crop plants (post-directed, lay-by treatment).

The application rates depend on the objective to be achieved, the timeof the year, the plants to be combated and their growth stage, and arefrom 0.01 to 5.0, preferably 0.05 to 3.0, kg of active ingredient perhectare.

The herbicidal action of the naphthindazoles of the formula I on thegrowthof test plants is illustrated by the following greenhouseexperiments.

The vessels employed were plastic flowerpots having a volume of 300 cm³and filled with a sandy loam containing about 3.0% humus. The seeds ofthe test plants were sown separately, according to species.

For the postemergence treatment, the plants were grown, depending ongrowthform, to a height of 3 to 15 cm before being treated. In thistreatment method, either plants which had been sown in the pots andgrown there wereselected, or they were cultivated separately asseedlings and transplanted to the pots a few days before being treatedwith the compounds suspended or emulsified in water. The applicationrates for postemergence treatment were 0.5 and 1.0 kg/ha.

The pots were set up in the greenhouse, species from warmer climates inwarmer areas (20° to 35° C.) and species from moderate climates at 10°to 20° C. The experiments were run for from 2 to 4 weeks. During thistime the plants were tended and their reactions to the varioustreatments assessed.

The assessment scale was 0 to 100, 100 denoting nonemergence or completedestruction of at least the visible plant parts, and 0 denoting nodamage or normal growth.

The plants used in the greenhouse experiments were Amaranthusretroflexus, Ipomoea spp., Setaria italica, Solanum nigrum and Veronicaspp.

The compounds of Examples 2, 4, 6, 45 and 59, applied postemergence atrates of 0.5 and 1.0 kg/ha, combated unwanted plants excellently.

In view of the number of application methods possible, the compoundsaccording to the invention, or agents containing them, may be used in afurther large number of crops for removing unwanted plants. Thefollowing crops are given by way of example:

    ______________________________________                                        Botanical name         Common name                                            ______________________________________                                        Allium cepa            onions                                                 Ananas comosus         pineapples                                             Arachis hypogaea       peanuts                                                                       (groundnuts)                                           Asparagus officinalis  asparagus                                              Avena sativa           oats                                                   Beta vulgaris spp. altissima                                                                         sugarbeets                                             Beta vulgaris spp. rapa                                                                              fodder beets                                           Beta vulgaris spp. esculenta                                                                         table beets, red                                                              beets                                                  Brassica napus var. napus                                                                            rapeseed                                               Brassica napus var. napobrassica                                                                     swedes                                                 Brassica napus var. rapa                                                                             turnips                                                Brassica rapa var. silvestris                                                 Camellia sinensis      tea plants                                             Carthamus tinctorius   safflower                                              Carya illinoinensis    pecan trees                                            Citrus limon           lemons                                                 Citrus maxima          grapefruits                                            Citrus reticulata      mandarins                                              Citrus sinensis        orange trees                                           Coffea arabica (Coffea canephora,                                                                    coffee plants                                          Coffea liberica)                                                              Cucumis melo           melons                                                 Cucumis sativus        cucumbers                                              Cynodon dactylon       Bermudagrass                                           Daucus carota          carrots                                                Elais guineensis       oil palms                                              Fragaria vesca         strawberries                                           Glycine max            soybeans                                               Gossypium hirsutum (Gossypium arboreum,                                                              cotton                                                 Gossypium herbaceum, Gossypium vitifolium)                                    Helianthus annuus      sunflowers                                             Helianthus tuberosus   Jerusalem artichoke                                    Hevea brasiliensis     rubber plants                                          Hordeum vulgare        barley                                                 Humulus lupulus        hops                                                   Ipomoea batatas        sweet potatoes                                         Juglans regia          walnut trees                                           Lactuca sativa         lettuce                                                Lens culinaris         lentils                                                Linum usitatissimum    flax                                                   Lycopersicon lycopersicum                                                                            tomatoes                                               Malus spp.             apple trees                                            Manihot esculenta      cassava                                                Medicago sativa        alfalfa (lucerne)                                      Mentha piperita        peppermint                                             Musa spp.              banana plants                                          Nicotiana tabacum (N. rustica)                                                                       tobacco                                                Olea europaea          olive trees                                            Oryza sativa           rice                                                   Panicum miliaceum      millet                                                 Phaseolus lunatus      limabeans                                              Phaseolus mungo        mungbeans                                              Phaseolus vulgaris     snapbeans, green                                                              beans, dry beans                                       Pennisetum glaucum     pearl millet                                           Petroselinum crispum spp. tuberosum                                                                  parsley                                                Picea abies            Norway spruce                                          Ables alba             fir trees                                              Pinus spp.             pine trees                                             Pisum sativum          English peas                                           Prunus avium           cherry trees                                           Prunus domestica       plum trees                                             Prunus dulcis          almond trees                                           Prunus persica         peach trees                                            Pyrus communis         pear trees                                             Ribes sylvestre        redcurrants                                            Ribes uva-crispa       gooseberries                                           Ricinus communis       castor-oil plants                                      Saccharum officinarum  sugar cane                                             Secale cereale         rye                                                    Sesamum indicum        sesame                                                 Solanum tuberosum      Irish potatoes                                         Sorghum bicolor (s. vulgare)                                                                         sorghum                                                Sorghum dochna         sorgo                                                  Spinacia oleracea      spinach                                                Theobroma cacao        cacao plants                                           Trifolium pratense     red clover                                             Triticum aestivum      wheat                                                  Triticum durum         durum wheat                                            Vaccinium corymbosum   blueberries                                            Vaccinium vitis-idaea  cranberries                                            Vicia faba             tick beans                                             Vigna sinensis (V. unguiculata)                                                                      cow peas                                               Vitis vinifera         grapes                                                 Zea mays               Indian corn, sweet                                                            corn, maize                                            ______________________________________                                    

To increase the spectrum of action and to achieve synergistic effects,the naphthindazoles of the formula I may be mixed and applied togetherwith numerous representatives of other herbicidal or growth-regulatingactive ingredient groups. Examples of suitable components are diazines,4H-3,1-benzoxazine derivatives, benzothiadiazinones,2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylicacids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils,benzofuran derivatives, cyclohexane-1,3-dione derivatives,quinolinecarboxylic acids,(het)aryloxyphenoxypropionic acids and salts,esters and amides thereof, etc.

It may also be useful to apply the novel compounds of the formula I,eitheralone or in combination with other herbicides, in admixture withother cropprotection agents, e.g., agents for combating pests orphytopathogenic fungi or bacteria. The compounds may also be mixed withsolutions of mineral salts used to remedy nutritional or trace elementdeficiencies. Non-phytotoxic oils and oil concentrates may also beadded.

We claim:
 1. A naphthindazole-4,9-quinone of the formula ##STR40## whereR¹ is C₂ -C₁₀ -alkyl, C₁ -C₁₀ -haloalkyl, C₁ -C₁₀ -hydroxyalkyl, C₂ -C₁₄-alkoxyalkyl, C₂ -C₁₄ -alkylthioalkyl, C₃ -C₇ -cycloalkyl, C₁ -C₄-alkylcarbonyloxy-C₁ -C₄ -alkyl, phenylaminocarbonyloxy-C₁ -C₄ -alkylwhich is unsubstituted or substituted in the phenyl moiety by halogen,C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, phenylsulfonyloxy-C₁ -C₄ -alkyl whichis unsubstituted or substituted in the phenyl moiety by halogen, C₁ -C₄-alkyl or C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxycarbonyl-C₁ -C₄-alkyl,hydroxycarbonyl-C₁ -C₄ -alkyl, aminocarbonyl-C₁ -C₄ -alkyl, C₁-C₄ -alkylaminocarbonyl-C₁ -C₄ -alkyl, di-(C₁ -C₄-alkyl)-aminocarbonyl-C₁ -C₄ -alkyl, halo-C₃ -C₄ -alkynyl, unsubstitutedor halogen- or C₁ -C₄ -alkyl-substituted heteroaryl radical with one ortwo nitrogen atoms, phenyl which is unsubstituted or substituted byhalogen, hydroxy, nitro, amino, C₁ -C₄ -alkylamino, di-C₁ - C₄-alkylamino, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkoxy,C₁ -C₄ -haloalkyl, C₁ -C₄ -alkylthio or C₁ -C₄ -haloalkylthio, orunsubstituted or halogen-substituted benzyl, andR², R³, R⁴ and R⁵ areidentical or different and each denotes hydrogen, halogen, nitro, cyano,hydroxy, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, C₁ -C₆-alkyl, C₁ -C₅ -haloalkyl, C₁ -C₅ -alkoxy, C₁ -C₅ -haloalkoxy, C₁ -C₅-alkylthio, C₁ -C₅ -haloalkylthio, C₂ -C₁₀ -alkoxyalkyl, carboxyl, C₂-C₆ -alkoxycarbonyl, C₂ -C₆ -alkanoyloxy, C₂ -C₆ -haloalkanoyloxy, C₁-C₄ -alkylcarbonylamino, C₁ -C₄ -alkylaminocarbonyl, di-(C₁ -C₄-alkyl-)aminocarbonyl, or phenyl or heteroaryl, each of which isunsubstituted or substituted by halogen, trifluoromethyl, nitro, cyano,amino, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio or C₁ -C₅ -haloalkylthio, andR³ and R⁴, together with the two carbon atoms of the phenyl ring towhich they are attached, form a heterocyclic ring or a benzene ornaphthalene ring which is unsubstituted or substituted by halogen,nitro, cyano, amino, hydroxy, trifluoromethyl, C₁ -C₅ -alkyl, C₁ -C₅-alkoxy, C₁ -C₅ -haloalkylthio, C₁ -C₅ -haloalkoxy or C₁ -C₅ -alkylthio.2. The naphthindazole-4,9-quinone of claim 1, wherein R¹ is C₂ -C₄-alkyl.
 3. The naphthindazole-4,9-quinone of claim 1, wherein R² to R⁵are identical or different and each denotes hydrogen, hydroxy orhalogen.
 4. The naphthindazole-4,9-quinone of claim 1, wherein R² is1-methylethyl and wherein R², R³, R⁴ and R⁵ are each hydrogen.
 5. Anaphthindazole-4,9-quinone of the formula ##STR41## where R¹ is C₁ -C₁₀-alkyl, C₁ -C₁₀ -haloalkyl, C₁ -C₁₀ -hydroxyalkyl, C₂ -C₁₄ -alkoxyalkyl,C₂ -C₁₄ -alkylthioalkyl, C₃ -C₇ -cycloalkyl, C₁ -C₄ -alkylcarbonyloxy-C₁-C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyloxy-C₁ -C₄ -alkyl,phenylaminocarbonyloxy-C₁ -C₄ -alkyl which is unsubstituted orsubstituted in the phenyl moiety by halogen, C₁ -C₄ -alkyl or C₁ -C₄-alkoxy, phenylsulfonyloxy-C₁ -C₄ -alkyl which is unsubstituted orsubstituted in the phenyl moiety by halogen, C₁ -C₄ -alkyl or C₁ -C₄-alkoxy, C₁ -C₄ -alkoxycarbonyl-C₁ -C₄ -alkyl, hydroxycarbonyl-C₁ -C₄-alkyl, aminocarbonyl-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyl-C₁ -C₄-alkyl, di-(C₁ -C₄ -alkyl)-aminocarbonyl-C₁ -C₄ -alkyl, halo-C₃ -C₄-alkynyl, unsubstituted or halogen- or C₁ -C₄ -alkyl-substitutedheteroaryl radical with one or two nitrogen atoms, phenyl which isunsubstituted or substituted by halogen, hydroxy, nitro, amino, C₁ -C₄-alkylamino, di-C₁ -C₄ -alkylamino, cyano, C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkylthio or C₁-C₄ -haloalkylthio, or unsubstituted or halogen-substituted benzyl,andR², R³, R⁴ and R⁵ are identical or different and each denoteshydrogen, halogen, nitro, cyano, hydroxy, amino, C₁ -C₄ -alkylamino,di-C₁ -C₄ -alkylamino, C₁ -C₆ -alkyl, C₁ -C₅ -haloalkyl, C₁ -C₅ -alkoxy,C₁ -C₅ -haloalkoxy, C₁ -C₅ -alkylthio, C₁ -C₅ -haloalkylthio, C₂ -C₁₀-alkoxyalkyl, carboxyl, C₂ -C₆ -alkoxycarbonyl, C₂ -C₆ -alkanoyloxy, C₂-C₆ -haloalkanoyloxy, C₁ -C₄ -alkylcarbonylamino, C₁ --C₄-alkylaminocarbonyl, di-(C₁ -C₄ -alkyl)-aminocarbonyl, or phenyl orheteroaryl, each of which is unsubstituted or substituted by halogen,trifluoromethyl, nitro, cyano, amino, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthioor C₁ -C₅ -haloalkylthio, and R³ and R⁴, together with the two carbonatoms of the phenyl ring to which they are attached, form a heterocyclicring or a benzene or naphthalene ring which is unsubstituted orsubstituted by halogen, nitro, cyano, amino, hydroxy, trifluoromethyl,C₁ -C₅ -alkyl, C₁ -C₅ -alkoxy, C₁ -C₅ -haloalkylthio, C₁ -C₅ -haloalkoxyor C₁ -C₅ -alkylthio.
 6. The naphthindazole-4,9-quinone of claim 5,where R¹ is C₂ -C₄ -alkyl or C₂ -C₄ -alkenyl.
 7. Thenaphthindazole-4,9-quinone of claim 5, wherein R² to R⁵ are identical ordifferent and each denotes hydrogen, hydroxy or halogen.
 8. Thenaphthindazole-4,9-quinone of claim 5, wherein R¹ is 1-methylethyl andwherein R², and R³ are each hydrogen.